JP3477723B2 - UV absorber and ultraviolet absorbing composition containing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel ultraviolet absorbers and ultraviolet absorbing compositions, and optical materials produced from the compositions, particularly intraocular lenses, contact lenses and spectacle lenses.

[0002]

2. Description of the Related Art Conventionally, salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based compounds, etc. have been known as ultraviolet absorbers for resins, and various compounds are selected and used according to the use and purpose. ing.

Conventionally, when an ultraviolet absorber is used by adding it to a polymerized composition, performance deterioration due to bleeding out from the polymerized composition and toxicity to the living body become a problem in the processing scene or use scene. Therefore, in order to improve such problems, a method of using an ultraviolet absorber having a polymerizable skeleton and homopolymerizing it or copolymerizing it with a polymerizable monomer is used. For example, 2,4-
A method of copolymerizing an ester of dihydroxybenzophenone and acrylic acid (Japanese Patent Publication No. 36-6771) with a polymerizable monomer has been reported. However, the maximum absorption wavelength of acrylates of benzophenone derivatives is relatively short, and the wavelength range (320-
It was insufficient to absorb (400 nm). Therefore, a benzotriazole-based UV absorber having a high UV absorption effect in the long wavelength region and having a longer maximum absorption wavelength, which is free from elution and bleed-out from the polymerization composition, has been desired. Also in these methods,
If the compatibility with the polymer is poor, the unreacted UV absorber may bleed out during polymerization or use, and the performance may be deteriorated or deteriorated. Also,
In the case where the UV absorber has poor compatibility in the polymerization composition, the UV absorber causes phase separation in the polymer, and the physical properties of the polymerization composition itself are deteriorated such as a decrease in transparency and a decrease in mechanical strength. was there.

On the other hand, it is well known that sunlight causes damage to the human eye, especially with regard to the formation of cataracts. The part of the sun that is most involved in this is the near-ultraviolet region of 300-400 nm. This ultraviolet (UV) band is known to cause eye damage by causing chemical changes in the lens and retina. The problem of eye damage caused by this near-ultraviolet light is especially great in aphakic patients. This is because the crystalline lens, which originally plays a role as a UV absorption filter, is extracted, so that it is susceptible to photochemical damage that can be caused by myopia. In order to avoid such problems and protect the human eye, as described in US Pat. No. 3,141,869, a UV absorber is used in a spectacle lens to prevent UV rays from reaching the eye. It was supposed to be mixed. For this purpose, a benzotriazole-based UV absorber is most suitable because a UV absorber having excellent UV-absorbing ability in the wavelength range of 300 to 400 nm is desired.

However, even in the case of such optical materials, particularly medical optical materials in the ophthalmological field, deterioration of physical properties due to the bleed-out and elution of the ultraviolet absorber and poor compatibility with the polymer as described above. Was a problem.
In particular, in the case of imparting ultraviolet absorbing ability to the oxygen permeable contact lens or the soft intraocular lens in order to protect the eye function and the eye tissue, since these are composed of a polymer containing a silicon atom, particularly a siloxane-containing polymer, Unlike conventional medical optical materials typified by PMMA, problems such as elution of an ultraviolet absorbent from a lens substrate, bleed-out, and deterioration of ultraviolet absorption characteristics are remarkable. That is, as can be seen from the fact that the glass transition point of silicone is lower than room temperature and that it is a rubber-like polymer at room temperature, the molecular motion of the siloxane region is large in the polymer of the siloxane compound, and the ultraviolet absorber existing in this part is large. Tended to bleed out and elute. For this reason, there is a safety problem due to the ultraviolet absorbing property disappearing after long-term use or the ultraviolet absorbent elutes. Further, as the content of the siloxane compound is increased in order to enhance the oxygen permeability and the flexibility, the problems of the above-mentioned safety and deterioration of the ultraviolet absorbing ability become more remarkable.

Also, particularly oxygen permeable contact lenses,
In medical materials such as soft intraocular lenses, since the material consists of a hydrophobic component such as silicone and a hydrophilic component that enhances biocompatibility, the added UV absorber is easy to phase separate, There was also a problem of deteriorating the physical properties.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and is 300 to 400.
It is an object of the present invention to provide an ultraviolet absorber having excellent ultraviolet absorbing ability in the wavelength region of nm, free from elution and bleed-out, and having good compatibility with a polymer, and a polymerized composition thereof.

[0008]

The present invention has a skeleton of a benzotriazole type ultraviolet absorber in the molecule, a polymerizable unsaturated double bond in the molecule, and is sandwiched between alkylene chains. Provided is an ultraviolet absorber having a urethane bond in the molecule. The present invention also provides an ultraviolet absorbing composition containing a polymer obtained by copolymerizing a monomer having a polymerizable unsaturated double bond in the molecule with the ultraviolet absorbent of the present invention. Further, the present invention provides
An optically transparent optical material comprising the above composition of the present invention is provided. The present invention also provides a hydrogel comprising the above composition of the present invention. Furthermore, the present invention provides a plastic film comprising the composition of the present invention. Furthermore, the present invention provides a coating material comprising the composition of the present invention.

Since the ultraviolet absorbent of the present invention has an alkylene chain through a urethane bond, it can improve the compatibility with many polymers, and is incorporated into the polymer through a covalent bond, and it contains a heavy chain containing the same. Ultraviolet absorption ability can be imparted to the coalescence. The urethane bond itself is a polar group, and the alkylene chain sandwiching the urethane bond has low polarity and is hydrophobic, and therefore the polarity of the entire ultraviolet absorber molecule can be controlled by adjusting the length of the alkylene chain. By doing so, optimum compatibility with many polymers can be obtained. As a result, the UV absorber reacts more completely with the polymer monomers, which can reduce the amount of unreacted monomer that can be extracted. The ultraviolet absorbent of the present invention has, in its molecule, a skeleton of a benzotriazole-based ultraviolet absorbent which is particularly excellent in ultraviolet absorbing ability in the wavelength region of about 300 to 400 nm. Here, the skeleton of the benzotriazole-based ultraviolet absorber means that the phenol ring is bonded to the 2-position nitrogen atom of the benzotriazole ring. Further, it has a polymerizable unsaturated double bond in the molecule, which enables copolymerization with another polymerizable monomer or homopolymerization by itself. And it makes it possible to give optimum compatibility with many polymers, that have a urethane bond sandwiched alkylene chain.

As a preferable example of the ultraviolet absorber of the present invention, 2- {2'-hydroxy-indicated by the following formula [I]:
5′-β- [N- (β- (meth) acryloyloxyalkyl) carbamoyloxy] alkoxyphenyl}-
2H-benzotriazole can be mentioned.

[0011]

[Chemical 2] (However, in the formula, R ¹ is H, halogen, or 1 to 1 carbon atoms.
A C 10 alkoxy group or a C 1-10 alkyl group, R ² is selected from the group consisting of H, CH ₃ and a C 1-10 alkyl group, and X is —O—R ³ —O. —CO—NH—R ⁴ —O—CO—C (R ⁵ ) ═CH ₂ (wherein R ³ and R ⁴ are C _{2 to} C ₂₀ alkylene groups which may be linear or branched). , And R ⁵ is H or CH ₃ )) Particularly preferred substances of the above structure are those in which R ¹ is an alkyl group, in particular CH ₃ , chlorine or CH ₃ O, R ² is t-butyl and X is R.
³ is —C ₂ H ₄ — or —C ₃ H ₆ — and R ⁴ is —C ₂ H ₄ — or —C ₃ H ₆ —. Among them, a particularly preferable compound is 2 represented by the formula [II]
-{2'-hydroxy-5 '-{β- [N- (β-methacryloyloxyethyl) carbamoyloxy] ethoxy} -3'-t-butylphenyl} -5-methyl-2H
-Benzotriazole.

[0012]

[Chemical 3] The ultraviolet absorber represented by the above formula [I] is obtained by reacting a phenol derivative having a desired R ² and —OR ³ OH with a nitroaniline having a desired R ¹ to give a nitrophenylazophenol derivative, which is then treated with an alkali. Phenyl-2H which has been processed to have the desired R ¹ , R ² and —OR ³ OH.
- After the triazole ^{derivative, OCN-R 4 -O-CO} -C (R 5) having the desired R ⁴ and R ⁵ to = C
It can be produced by reacting an isocyanate derivative represented by H ₂ . These individual steps are
It can be carried out based on a known organic chemical reaction, and preferable specific conditions are described in detail in the examples below.

The UV absorber of the present invention can be copolymerized with many unsaturated monomers to provide a composition having desired UV absorbing properties. The ultraviolet absorbing composition of the present invention may be composed only of the homopolymer or copolymer of the ultraviolet absorbent of the present invention, and may further contain other polymer and / or various additives and colorants. . That is, since the homopolymer or copolymer of the ultraviolet absorbent of the present invention imparts ultraviolet absorption characteristics, it can be used as an additive for a wide range of polymers. Representative polymers and copolymers suitable for containing the ultraviolet absorber of the present invention as a copolymerization component, and representative polymers and copolymers suitable for blending with the ultraviolet absorbing polymer include There are the following.

(1) Polymers derived from mono- or diolefins: for example, polyethylene, polypropylene, polyisoprene, polyisobutylene, polymethylbutene-1, polymethylbutene-1, which may be optionally crosslinked.
1, polyisobutylene, polybutadiene, poly-4-methylpentene.

(2) Mixtures of homopolymers mentioned in (1): polypropylene and polyethylene, polypropylene and polyisobutene, polypropylene and polybutene-1.

(3) Copolymer of monomers based on the polymers listed in (1): for example, ethylene-chloropyrene copolymer,
Propylene-butene-1 copolymer, propylene-isobutylene copolymer, ethylene-butene-1 copolymer, and diene of ethylene and propylene, for example, hexadiene, dicyclopentadiene, terpolymer of ethylidene norbornene, And alpha-olefins such as copolymers of ethylene and (meth) acrylic acid.

(4) Copolymer of styrene or α-methylstyrene: For example, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile- (meth) acrylic acid ester copolymer, impact strength Styrene-acrylonitrile copolymers and block copolymers modified with acrylic acid ester polymers for application, such as styrene-butadiene-styrene block copolymers.

(5) Graft copolymers of styrene: For example, graft copolymers of styrene onto polybutadiene, generally acrytonitrile-butadiene-styrene or AB.
Graft copolymer of styrene and acrylonitrile onto a mixture of polybutadiene called S resin and the copolymer listed in (4) and polybutadiene.

(6) Silicone polymers such as polyorganosiloxane.

(7) Halogen-containing vinyl polymer: For example,
Polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, polychloroprene, rubber chloride, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinylidene chloride-vinyl acetate copolymer.

(8) α, β-unsaturated organic acids and their derivatives: esters of polyacrylic acid and polymethacrylic acid, hydroxyethyl polymethacrylate, polyacrylamide and polyacrylonitrile. The UV absorbers according to the invention can advantageously be used in thermosetting acrylic resin lacquers and copolymers of (meth) acrylic acid and one or more derivatives thereof and melamine-formaldehyde resins.

(9) Polymers derived from unsaturated alcohols and amines, and acyl polymers thereof, such as polyvinyl alcohol, polyvinyl acetate, vinyl polystearate, vinyl polybenzoate, vinyl polymaleate, polyvinyl butyral, polyphthalate. Copolymers with allyl acid, polyallyl melamine and other vinyl compounds. For example, ethylene-vinyl acetate copolymer.

(10) Homopolymers and copolymers derived from epoxides: for example, polymers derived from polyethylene oxide or bisglycidyl ether.

(11) Polyacetal: For example, polyoxymethylene, and polyoxymethylene containing ethylene oxide as a copolymer.

(12) Polyalkylene oxide: for example, polyoxyethylene, polypropylene oxide or polybutylene oxide.

(13) Polyphenylene oxide (14) Polyurethanes and polyureas (15) Polycarbonates (16) Polysulfones (17) Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams: eg , Polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12, m-vinyl lactam and poly-m-phenylene-isophthalamide.

(18) Polyesters derived from dicarboxylic acids and dialcohols and / or from hydroxysulfonic acids or the corresponding lactones: eg polyethylene glycol terephthalate, poly-1,4-dimethylcyclohexane terephthalate.

(19) Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand: for example phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde.

(20) Alkyd resin: for example, glycerin-
Phthalates and their mixtures with melamine-formaldehyde resins.

(21) Unsaturated polyesters derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols and also from vinyl compounds as crosslinking agents and also halogen-containing flame-retardant modifications thereof.

(22) Natural polymer: for example, cellulose,
Rubber.

(23) A chemically modified homologous derivative of (22): cellulose acetate, cellulose propionate,
And cellulose acetate and cellulose ethers such as methyl cellulose.

Particularly useful compositions are the UV absorbers according to the invention and, for example, styrene, methylstyrene, compounds containing silicon atoms and unsaturated double bonds, acrylates,
Methacrylic acid ester, acrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride,
It includes a copolymer with another monomer having a copolymerizable unsaturated double bond such as vinylidene chloride, vinylidene fluoride, vinyl fluoride, vinyl lactam, ethylene, propylene and a mixture thereof.

The preferred polymer contained in the composition of the present invention is one containing a silicon atom. Here, the polymer containing a silicon atom may be a polymer containing a silicon atom in the main chain and / or side chain of the polymer, and is, for example, a polymer containing a siloxane bond or an organic silane group such as a trimethylsilyl group. It is a polymer as a component. In these polymers containing a silicon atom, a long-chain polymer in which a silicon atom is contained in a polymer through a siloxane bond is preferable from the viewpoint of oxygen permeability and / or flexibility. Specific examples of such a polymer include tris (trimethylsiloxy) silylpropyl methacrylate, polydimethylsiloxane having a double bond at both ends, a homopolymer using a silicone-containing (meth) acrylate, or a homopolymer of these monomers and other monomers. Examples include copolymers with monomers. The copolymerizable monomers include (meth) acrylic monomers, aromatic vinyl monomers, monofunctional monomers such as heterocyclic vinyl monomers,
Alternatively, polyfunctional monomers such as di-, tri-, tetra- (meth) acrylic monomers, aromatic divinyl monomers, aromatic diallyl monomers and the like can be mentioned. Examples of the (meth) acrylic monomer include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxybutyl ( Hydroxyalkyl (meth) acrylates such as (meth) acrylates, halogenated alkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, tetrafluoroethyl (meth) acrylate, cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate ) Examples include acrylates. Above all, the use of methyl methacrylate provides good mechanical properties. Further, it is preferable to use a fluoroalkyl (meth) acrylate from the viewpoint that a polymer satisfying both functions of oxygen permeability and mechanical properties can be obtained. Examples of the aromatic vinyl monomer include vinylbenzene, vinylnaphthalene, vinylethylbenzene and the like. Further, examples of the heterocyclic vinyl monomer include vinylcarbazole, maleimide, maleic anhydride and the like. As these copolymerizable monomers, (meth) acrylate monomers are preferable from the viewpoint of copolymerizability and transparency. Among them, methyl (meth) is advantageous in terms of mechanical properties, transparency, and oxygen permeability.
Most preferred are acrylate, trifluoroethyl (meth) acrylate, (meth) acrylic acid. The copolymerizable polyfunctional monomer will be described. Examples of di (meth) acrylic monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate and urethane-modified di (meth) acrylate. ) Acrylate,
Propylene glycol di (meth) acrylate, glycerol di (meth) acrylate, neopentyl glycol di (meth) acrylate and the like can be mentioned. Examples of tri (meth) acrylic monomers include trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate. Examples of the tetra (meth) acrylic monomer include tetramethylolmethane tetra (meth) acrylate. Examples of the aromatic divinyl compound include o-, m-, and p-diallyl phthalates. Examples of other polyfunctional monomers include bismaleimide and allyl (meth) acrylate. Di-, tri-, tetra-, and (meth) acrylate monomers are preferable in terms of copolymerizability and transparency. Of these, tri (meth) acrylate is most preferable from the viewpoint of mechanical properties and transparency.

From the above, from the viewpoint of transparency, oxygen permeability and mechanical properties, a polymer containing a silicon atom,
Most preferably, it is a copolymer of a siloxane compound having a double bond and a compound having a (meth) acryloyl group.

When a polymer containing a silicon atom and a copolymerizable monomer are copolymerized, the respective compositions are usually 10 to 90 parts by weight of the polymer containing a silicon atom and 10 to 90 parts of the copolymerizable monomer. It is selected in the range of 90 parts by weight, but is not particularly limited. When the amount of the polymer containing a silicon atom is 9 parts by weight or less, the oxygen permeability is insufficient, and when it is 91 parts by weight or more, the strength decreases.
It may not be preferable. Generally, in a copolymer of a polymer containing a silicon atom and another monomer, as the proportion of the polymer containing a silicon atom increases, the oxygen permeability tends to increase and the strength tends to decrease.

The presence of silicon atoms in the polymer may be uniform throughout the polymer or in a heterogeneous system having a so-called microphase-separated structure.

The oxygen permeability coefficient of the above composition containing silicon atoms is 10 × 10 ⁻¹¹ cm ³ (STP) · cm / cm ² · sec · mmHg.
The above is preferable. The oxygen permeability coefficient here is measured by a known method such as an electrode method vacuum method or a pressure method. When the ultraviolet absorbing composition of the present invention is applied to a contact lens, the oxygen transmission coefficient is 10 × 10 ^−11.
If it is smaller than cm ³ (STP) ・ cm / cm ²・ sec ・ mmHg, it will not be possible to supply enough oxygen to the cornea from the surface of the cornea through the lens, and the physiological burden on the cornea when worn for a long period of time. Is large, which is not preferable. In addition, continuous wearing causes undesired corneal edema, which may cause visual impairment. The concentration of the added ultraviolet absorber is 0.01 to 1 with respect to the weight of the mixed liquid of the raw material monomers.
A range of 0% by weight is desirable. If the concentration is 0.01% by weight or less, sufficient ultraviolet absorption ability cannot be obtained. Further, if the addition amount exceeds 10% by weight, the polymerization rate and the mechanical strength may decrease, which is not preferable. 200-40 for contact lenses and intraocular lenses
It is desirable that the transmittance at the maximum absorption wavelength in the ultraviolet region of 0 nm is less than 20%. To obtain this, a proper concentration of the ultraviolet absorber is determined in consideration of the thickness of the lens.

Since the ultraviolet absorbing composition of the present invention does not transmit a short wavelength, it can be widely used as an optical material as a cut filter. When used for optical materials,
The ultraviolet absorber may be used alone, or a colorant may be added to adjust the absorption characteristics in the visible light region. As the coloring agent used, direct dyes, oil-soluble dyes, acid dyes, basic dyes, disperse dyes, vat dyes, monoazo-based bisazo-based organic pigments, bisazo-based, anthraquinone-based, quinonaphthalone-based, xanthene-based, pyrazole-based,
Examples thereof include triphenylmethane-based, indigoid-based, fluorane-based, and quinoline-based organic dyes, but are not limited thereto.

When the ultraviolet absorbing composition of the present invention is used as an optical material, in addition to medical optical materials such as spectacle lenses, intraocular lenses and contact lenses, condenser lenses for spectrophotometers,
Optical fibers, solar energy collectors, fluorescent diffusers and the like can be mentioned, but particularly suitable ones are contact lenses,
It is an intraocular lens.

The UV absorbing composition of the present invention can also be in the form of a hydrogel. Where “hydrogel”
Means a crosslinked polymer having an equilibrium water content of about 10-90%. Examples of monomers that give this hydrogel include hydroxy lower alkyl (C ₁ -C ₉ ).
(Meth) acrylate, which is the corresponding (meth) acrylate
A hydrogel is cross-linked with a few percent of an acrylate diester, such as ethylene glycol dimethacrylate.
Examples of other suitable hydrophilic monomers are N-vinyl heterocyclic monomers, examples of which include N-vinyl-2-pyrrolidone, N-vinyl pyridine and N-vinyl caprolactam. . In addition, examples of other hydrophilic monomers are polymerizable olefinic acids and amides,
Suitable examples include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, acrylamide, methacrylamide and N- (1,1-dimethyl-3-oxobutylacrylamide). Another suitable group of hydrophilic monomers are the lower alkyl vinyl ethers such as methyl and ethyl vinyl ethers. The preferred UV absorbing hydrogel in the present invention is a copolymer with hydroxyethyl methacrylic acid. The hydrogel can be preferably used as a soft contact lens or an intraocular lens.

The UV absorbing composition of the present invention can also be in the form of a plastic film, which is applicable to transparent plastic films, packaging materials, vinyl window coatings, interior covers and the like.

The UV absorbing composition of the present invention can also be used as a coating material, which can be applied to polymer coating, automobile paint, interior coating, spectacle lens coating and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.

[0045]

【Example】

Example 1 2- {2′-hydroxy-5 ′-{β- [N- (β-methacryloyloxyethyl) carbamoyloxy] ethoxy} -3′-t-butylphenyl} -5-methyl-2
Synthesis of H-benzotriazole First, the intermediate 2-t-butyl-4- (2'-hydroxyethoxy) phenol was synthesized as follows.

In a 500 ml three-necked flask equipped with a mechanical stirrer and a Dimroth condenser, t-butyl hydroquinone (42.8 g) was added to 150 g under an argon atmosphere.
Dissolve in ml methanol and add 10.3 g sodium hydroxide, 50 ml water, 20.6 g 2-chloro-1-ethanol and 0.3 g potassium iodide to this solution.
This solution was heated under reflux for 24 hours, and then the reaction solution was allowed to cool to room temperature and diluted with 300 ml of water. The product was extracted from this solution with dichloromethane. After drying with anhydrous sodium sulfate, the solvent was distilled off, and the product was recrystallized from toluene for purification to obtain 15.3 g of the product.

Then, the intermediate 2-t-butyl-4-
(2'-hydroxyethoxy) -6- (4'-methyl-
The synthesis of 2-'nitrophenylazo) -phenol was performed as follows.

500 ml with mechanical stirrer
In a three-necked flask, 8.2 g of 98% 4-methyl-2-nitroaniline and 18 ml of concentrated hydrochloric acid were stirred and dissolved at room temperature. The solution was diluted with 50 ml ice water. While this solution was cooled with ice and kept at 4 ° C. or lower, 3.8 g of 97% sodium nitrite dissolved in 15 ml of water was added dropwise. After completion of dropping, the mixture was stirred for 1 hour while continuing to cool. Then, sulfamic acid was added until bubbles were not generated, and excess sodium nitrite was decomposed. This reaction liquid was filtered to obtain a filtrate. 10.7 g of 2-t-butyl-4- (2'-hydroxyethoxy) phenol and 6 g of sodium hydroxide dissolved in 200 ml of water was added to the above filtrate while cooling with ice and keeping the temperature below 4 ° C while stirring. Was dripped. After adding about 1/3 of the diazonium solution, 40 ml of a 10% sodium hydroxide aqueous solution was simultaneously added dropwise. The reaction solution was subsequently stirred at 4 ° C. or lower for 2 hours and then left to stand at room temperature. Hydrochloric acid was added to acidify to obtain crystals of the azo dye,
Separated by filtration.

Then, 2- [2'-hydroxy-5'-
The synthesis of {β-hydroxyethoxy} -3′-t-butylphenyl] -5-methyl-2H-benzotriazole was performed as follows.

2-t-butyl-4-obtained above
(2'-hydroxyethoxy) -6- (4'-methyl-
150 g of 2-'nitrophenylazo) -phenol in a 500 ml three-necked flask equipped with a mechanical stirrer.
It was dissolved in ml of ethanol. Under argon atmosphere, at room temperature, a solution prepared by dissolving 18 g of glucose in 150 ml of 2N aqueous sodium hydroxide solution was added dropwise while keeping the temperature at 30 ° C. or lower. To this reaction solution, 12 g of zinc powder was added little by little. The reaction solution was stirred at room temperature for 4 hours and then diluted with 100 ml of water. The generated precipitate was separated by filtration and washed with water. The precipitate was washed with ethanol to dissolve the product and separate it from zinc. Ethanol was distilled off with an evaporator, and the product was dried under vacuum. The product was recrystallized from heptane and purified to give 9.4 g of product.

2- {2'-hydroxy-5 '-{β-
[N- (β-methacryloyloxyethyl) carbamoyloxy] ethoxy} -3′-t-butylphenyl}-
Synthesis of 5-methyl-2H-benzotriazole 2- [2'-hydroxy-5 '-{β-hydroxyethoxy} -3'-t-butylphenyl] -5-methyl-in a 300 ml three-necked flask equipped with a Dimroth condenser. 2.4 g of 2H-benzotriazole, 50 ml of tetrahydrofuran, di-n-butyltin dilaurate 1
0 μl and 10 mg of hydroquinone were taken and stirred at 60 ° C. with a magnetic stirrer. To this, 1.52 g of methacryloyloxyethyl isocyanate was added dropwise. Stirring was continued at 60 ° C. for 9 hours, and after confirming the disappearance of methacryloyloxyethyl isocyanate by thin layer chromatography, the reaction was terminated and tetrahydrofuran was distilled off. The solid content was dissolved in diethyl ether, washed with water, the ether layer was collected, and the ether was distilled off. The solid content was dissolved in 120 ml of methanol + 60 ml of dichloromethane and purified by recrystallization to obtain 2.6 g of a product. The melting point of this purified product was 105 ° C.

FIG. 1 shows the ultraviolet-visible absorption spectrum of this ultraviolet absorber. As shown in the spectrum, a sufficiently large absorption was obtained in the ultraviolet region. Moreover, the infrared absorption spectrum of this ultraviolet absorber is shown in FIG.

Example 2 53.4 parts by weight of 2,6-diisocyanatocaproic acid-β-isocyanatoethyl ester was placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet. 52 parts by weight of 2-hydroxyethyl methacrylate,
0.01 parts by weight of di-n-butyltin dilaurate was charged, and the mixture was stirred at 50 ° C. under a nitrogen atmosphere until the absorption of hydroxyl groups disappeared in the infrared absorption spectrum. Average molecular weight 94
94.6 parts by weight of an alcohol-modified polydimethylsiloxane represented by the following formula having 6 are added to the four-necked flask at 50 ° C. until the absorption of the isocyanate group in the infrared absorption spectrum disappears. Stir under a nitrogen atmosphere,
A reaction product containing a siloxane macromer represented by the following formula [III] as a main component and having two double bonds at each end was obtained.

[0054]

[Chemical 4] This reaction product (main component is siloxane macromer) 10
3 parts by weight of trifluoroethyl methacrylate
In addition to the addition by weight, 0.055 parts by weight of trimethylolpropane trimethacrylate and 0.004 parts by weight of azobismethylvaleronitrile were added. UV absorber 2- {2'-hydroxy-5 against this monomer mixture
′-{Β- [N- (β-methacryloyloxyethyl)
Carbamoyloxy] ethoxy} -3′-t-butylphenyl} -5-methyl-2H-benzotriazole.
5% by weight was added, and each composition was mixed and dissolved to obtain a uniform transparent stock solution. Degas this stock solution in a glass rod,
After nitrogen atmosphere, it was sealed. 40 in a constant temperature water bath
℃, 40 hours, 50 ℃, 24 hours, 60 ℃, 16 hours,
The reaction was carried out at 70 ° C. for 4 hours, 90 ° C. for 2 hours. Further, heating was carried out at 130 ° C. for 3 hours in a circulation dryer to obtain a rod-shaped polymer. The obtained polymer had a Shore D hardness of 74 and was hard, and had good machinability and polishability and good machinability.

This polymer was made into small pieces with a mixer, and 1 g of this small piece was immersed in 50 g of distilled water and kept at 100 ° C. for 30 minutes.
It was extracted by heating for an hour. No elution of the ultraviolet absorber was observed spectroscopically in this extract.

This polymer was processed into a disk having a diameter of 17 mm and a thickness of 5 mm and heat-treated under reduced pressure at 120 ° C. for 16 hours, but no change in color tone or absorbance due to bleed-out was observed.

The polymer is 9 mm in diameter and 0.2 mm in thickness.
After being processed into a disk of No. 1, the mixture was heat-treated under reduced pressure at 120 ° C. for 16 hours. This disc was subjected to an irradiation test with a fade meter at room temperature. Irradiation with a fade meter Even after 200 hours of irradiation, the absorbance is 9 times that before the irradiation.
5.8% was observed, and there was no deterioration in the ultraviolet absorption capacity, indicating excellent light resistance.

The oxygen permeation coefficient of this polymer was 32 × 10 ⁻¹¹ cm ³ (STP) · cm / cm ² · sec · mmHg at 37 ° C., which was determined by using a Kaken type film oxygen permeation meter.
Met.

This polymer was cut and polished to give a lens system 9.0.
mm, base curve 8.0 mm, lens power -3.0
It was possible to process it into a 0D contact lens.

Example 3 50 parts by weight of tris (trimethylsiloxy) silylpropyl methacrylate, 5 parts of trifluoroethyl methacrylate
0 parts by weight, 0.05 parts by weight of azobisisobutylnitrile and 0.15 parts by weight of azobiscyclohexanecarbonitrile were mixed to prepare a polymerization stock solution. 2- {2'-hydroxy-5 'as an ultraviolet absorber for this monomer mixture
-{Β- [N- (β-methacryloyloxyethyl) carbamoyloxy] ethoxy} -3′-t-butylphenyl} -5-methyl-2H-benzotriazole was added to 0.
5% by weight was added and dissolved to obtain a uniform transparent stock solution. After dissolution, the mixture was sealed in a test tube, heated from 60 ° C. to 110 ° C. over 24 hours, and then held at 110 ° C. for 4 hours to obtain a polymer.

This polymer was made into small pieces with a mixer, and 1 g of the small pieces was dipped in 50 g of distilled water and kept at 100 ° C. for 30 minutes.
It was extracted by heating for an hour. No elution of the ultraviolet absorber was observed spectroscopically in this extract.

This polymer was processed into a disk having a diameter of 17 mm and a thickness of 5 mm, and then heat-treated under vacuum reduced pressure at 120 ° C. for 16 hours, and the decrease in absorbance due to bleeding out was examined spectroscopically. As a result, changes in color tone and absorbance due to bleed-out were not observed.

The polymer is 9 mm in diameter and 0.2 mm in thickness.
After being processed into a disk of No. 1, the mixture was heat-treated under reduced pressure at 120 ° C. for 16 hours. This disc was subjected to an irradiation test with a fade meter at room temperature. Irradiation with a fade meter Even after 200 hours of irradiation, the absorbance is 9 times that before the irradiation.
7.2% was observed, and there was no deterioration in the ultraviolet absorbing ability, and excellent light resistance was exhibited.

The oxygen permeation coefficient of this polymer was 30 × 10 ⁻¹¹ cm ³ (STP) · cm / cm ² · sec · mmHg at 37 ° C., which was determined by a Seikaken film oxygen permeation meter.
Met.

This polymer has good machinability, and was cut and polished to give a lens system of 9.0 mm and a base curve of 8.0 m.
m, and a lens power of −3.00D could be processed.

Example 4 Polydimethylsiloxane 45 having double bonds at both ends
Parts by weight, 47.5 parts by weight of trifluoroethyl methacrylate, 3 parts by weight of methacrylic acid, and 4.5 parts by weight of trimethylolpropane trimethacrylate are uniformly mixed, and 0.05 parts by weight of azobisisobutyronitrile, azo 0.15 parts by weight of biscyclohexylcarbonitrile was added. 2- {2'-hydroxy-5 '-{β- [N- (β-methacryloyloxyethyl) carbamoyloxy] ethoxy} -3'-t-butylphenyl} -as an ultraviolet absorber for this monomer mixture 5-methyl-2
0.5% by weight of H-benzotriazole was added, and each composition was mixed and dissolved to obtain a uniform transparent stock solution. This stock solution was placed in a rod-shaped glass container, degassed, made into a nitrogen atmosphere, and then sealed. This was heated from 60 ° C. to 110 ° C. over 24 hours and then held at 110 ° C. for 4 hours to obtain a polymer. The obtained polymer had a Shore D hardness of 70 and was hard, and had good machinability and polishability.

This polymer was made into small pieces with a mixer, and 1 g of this small piece was immersed in 50 g of distilled water and kept at 100 ° C. for 30 minutes.
It was extracted by heating for an hour. The elution of the ultraviolet absorber in this extract was observed spectroscopically. As a result, no elution of the ultraviolet absorber was observed spectroscopically.

This polymer was processed into a disk having a diameter of 17 mm and a thickness of 5 mm and then heat-treated under vacuum reduced pressure at 120 ° C. for 16 hours, and the decrease in absorbance due to bleed-out was examined spectroscopically. As a result, changes in color tone and absorbance due to bleed-out were not observed.

The polymer is 9 mm in diameter and 0.2 mm in thickness.
After being processed into a disk of No. 1, the mixture was heat-treated under reduced pressure at 120 ° C. for 16 hours. This disc was subjected to an irradiation test with a fade meter at room temperature. Irradiation with a fade meter Even after 200 hours of irradiation, the absorbance is 9 times that before the irradiation.
5.2% was recognized, and there was no deterioration in the ultraviolet absorbing ability, and excellent light resistance was exhibited.

The oxygen permeation coefficient of this polymer was 130 × 10 ⁻¹¹ cm ³ (STP) · cm / cm ² · sec · mm at 37 ° C., which was determined by a Seikaken film oxygen permeation meter.
It was Hg.

This polymer was cut and polished to have a lens diameter of 9.0.
mm, base curve 8.0 mm, lens power -3.0
It was possible to process it into a 0D contact lens.

FIG. 3 shows an ultraviolet-visible absorption spectrum (transmittance) of a disk having a thickness of 0.2 mm. As shown in the spectrum, a sufficiently large absorption was obtained in the ultraviolet region.

This polymer was cut and polished to give a lens system 9.0.
mm, base curve 7.0 mm, lens power -3.0
It was processed into a 0D contact lens. This lens was continuously worn for 15 days in 10 Japanese white rabbits, and a rabbit eye mucous membrane irritation test was performed by the Draize method.
The contact lens was worn on one eye, and the other eye was not worn. As a result, even after continuous wear for 15 days, corneal opacity / edema, eyelid conjunctival hyperemia / edema, bulbar conjunctival hyperemia / edema, and secretions were mild. The total score by the Draize method was judged to be non-irritating to the ocular mucosa in the wearing eye 2.1, the non-wearing eye 1.7 and the wearing eye. As a result, the present contact lens could be safely continuously worn.

From the results of Examples 1, 2, 3, and 4, the ultraviolet absorbent obtained by the present invention is excellent in ultraviolet absorbing ability in the wavelength region of 300 to 400 nm, has no elution or bleed-out, and is compatible with the polymer. It is a highly soluble UV absorber,
As a result, the polymerization composition has a stable ultraviolet absorption ability,
It turns out that it can be used for a wide range of purposes.

[0075]

According to the present invention, there is provided an ultraviolet absorber excellent in ultraviolet absorbing ability in the wavelength region of 300 to 400 nm, free from elution and bleed out, and having good compatibility with a polymer, and a polymerized composition thereof. You can

[Brief description of drawings]

FIG. 1 is an ultraviolet-visible absorption spectrum of an ultraviolet absorbent of the present invention obtained in an example.

FIG. 2 is an infrared absorption spectrum of the ultraviolet absorbent of the present invention obtained in an example.

FIG. 3 is an ultraviolet-visible absorption spectrum (transmittance) of the polymers obtained in Examples.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08J 5/18 C08J 5/18 C09D 183/08 C09D 183/08 G02C 7/04 G02C 7/04 (56) References 60-166369 (JP, A) JP 63-185969 (JP, A) JP 3-257420 (JP, A) JP 52-84258 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09K 3/00 104 C07D 249/18-249/20 C08F 220/36 C08F 246/00 C08G 77/388 C08J 5/18 C09D 183/08 C02C 7/04

Claims (15)

(57) [Claims] 1. The formula [I]: (However, in the formula, R ¹ is H, halogen, or 1 to 1 carbon atoms.
A C 10 alkoxy group or a C 1-10 alkyl group, R ² is selected from the group consisting of H, CH ₃ and a C 1-10 alkyl group, and X is —O—R ³ —O. ^{-CO-NH-R 4 -O-} CO-C (R
⁵ ) = CH ₂ (wherein R ³ and R ⁴ are C _{2 to} C ₂₀ alkylene groups which may be linear or branched and R ⁵ is H or CH ₃ )) ultraviolet absorbers that will be. 2. A UV absorber according to claim 1 R ¹ is an alkyl group. 3. A UV absorber according to claim 1, wherein R ¹ is CH _3. 4. The ultraviolet absorber according to claim 1, wherein R ² is t- butyl group. 5. 2- {2'-hydroxy-5 '-{β-
[N- (β-methacryloyloxyethyl) carbamoyloxy] ethoxy} -3′-t-butylphenyl}-
Is 5-methyl -2H- benzotriazole claim 1
The ultraviolet absorber described. 6. A UV absorbing composition containing a polymer obtained by copolymerizing the UV absorbent according to claim 1 with a monomer having a polymerizable unsaturated double bond in the molecule. 7. The ultraviolet absorbing composition according to claim 6 , wherein the polymer is a polymer containing a silicon atom. 8. An oxygen permeability coefficient of 10 × 10 ^-11 cm ³ (STP).
cm / cm ² · sec · mmHg or more
7. The ultraviolet absorbing composition according to 7 . 9. An ultraviolet absorber in an amount of 0.05 to 10.0% by weight.
The ultraviolet absorbing composition according to claim 6, which contains. 10. An optically transparent optical material comprising the composition according to claim 6 . 11. The optical material according to claim 10, which is a contact lens, an intraocular lens or a spectacle lens. 12. A hydrogel comprising the composition according to claim 6 . 13. hydrogel-forming monomers, hydroxyalkyl meth click relays DOO, hydroxyalkyl acrylates les <br/> over preparative, N- vinyl heterocyclic monomers chromatography, polymerizable olefinic
Acid, polymerizable olefinic Ami de, and claim 1 is selected from alkyl vinyl ether or Ranaru group having 1 to 5 carbon atoms
2. The hydrogel as described in 2 . 14. A plastic film comprising the composition according to claim 6 . 15. A coating material comprising the composition according to claim 6 .